Cyclopropanecarboxylic acid esters and pest controllers containing the same

ABSTRACT

A 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl 2,2-dimethyl-3-(2-cyano-3-hydrocarbyloxy-3-oxo-1-propenyl) cyclopropanecarboxylate given by the formula (1): 
                         
wherein G represents C1–C4 alkyl or C3–C4 alkenyl, has excellent pests controlling effect.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a section 371 of International Application No.PCT/JP03/12093, filed Nov. 20, 2003, the disclosure of which isincorporated herein by reference.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to an novel cyclopropanecarboxylic acidester and uses thereof.

BACKGROUND ART

As acid parts of natural pyrethroid compounds, two acids, one whosesubstituent at 3-position on the cyclopropane ring is the2-methyl-1-propenyl and another whose substituent is2-methyl-3-methoxy-3-oxo-1-propenyl, are known. The synthetic pyrethroidcompounds, wherein the methyl at 2-position on the2-methyl-3-methoxy-3-oxo-1-propenyl is replaced with a halogen atom, aredescribed in U.S. Pat. No. 4,939,172, GB patent publication 2,268,740and the like. However the pests controlling activity of these compoundsis sometimes shortly, then it is desired to develop the compounds havingenough activity for controlling pests.

DISCLOSURE OF THE INVENTION

The present inventor has earnestly studied for seeking the compoundhaving excellent pests controlling activity, and found thatcyclopropanecarboxylic acid esters substituted at 3-position on thecyclopropane ring with 2-cyano-3-hydrocarbyloxy-3-oxo-1-propenyl givenby the following formula (1) has excellent pests controlling effect tocomplete the present invention.

The present invention provides 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-(2-cyano-3-hydrocarbyloxy-3-oxo-1-propenyl)cyclopropanecarboxylate (hereinafter, referred to as the presentcompound) given by the formula (1):

wherein G represents C1–C4 alkyl or C3–C4 alkenyl; furthermore, apesticidal composition containing the present compound as an effectiveingredient, and a method of controlling pests comprising applying aneffective amount of the present compound to pests or the habitat ofpests.

In the present invention, the C1–C4 alkyl represented G includes, forexample, methyl, ethyl, propyl, 1-methylethyl and 1,1-dimethylethyl; theC3–C4-alkenyl includes, for example, allyl.

Embodiments for the present invention include, for example,

-   the compound wherein the absolute configuration at 1-position on the    cyclopropane ring is R-configuration in the formula (1); the    compound wherein the relative configuration between the substituents    at 1-position and 3-position on the cyclopropane ring is    trans-configuration in the formula (1);-   the compound wherein the absolute configuration at 1-position on the    cyclopropane ring is R-configuration, and the relative configuration    between the substituents at 1-position and 3-position on the    cyclopropane ring is trans-configuration in the formula (1);-   the compound wherein the absolute configuration at 1-position on the    cyclopropane ring is R-configuration with 90% or more ratio in the    formula (1);-   the compound wherein the relative configuration between the    substituents at 1-position and 3-position on the cyclopropane ring    is trans-configuration with 90% or more ratio in the formula (1);-   the compound wherein the absolute configuration at 1-position on the    cyclopropane ring is R-configuration, and the relative configuration    between the substituents at 1-position and 3-position on the    cyclopropane ring is trans-configuration, with 90% or more ration in    the formula (1);-   the compound wherein the absolute configuration at 1-position on the    cyclopropane ring is R-configuration with 80% or more ratio in the    formula (1);-   the compound wherein the relative configuration between the    substituents at 1-position and 3-position on the cyclopropane ring    is trans-configuration with 80% or more ratio in the formula (1);-   the compound wherein the absolute configuration at 1-position on the    cyclopropane ring is R-configuration, and the relative configuration    between the substituents at 1-position and 3-position on the    cyclopropane ring is trans-configuration, with 80% or more ration in    the formula (1).

The present compound can be produced, for example, by making4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-formylcyclopropanecarboxylate given by the formula (2):

react with a cyanoacetic acid ester given by formula (3):

wherein G has the same meaning as defined above.

The reaction is usually carried out in a solvent, in the presence of acarboxylic acid salt.

The solvent utilized in the reaction includes, for example, aromatichydrocarbons such as benzene, toluene, xylene and the like.

The carboxylic acid salt utilized in the reaction includes, for example,alkali metal salts of carboxylic acid such as sodium acetate, potassiumacetate, sodium benzoate and the like, and ammonium salts of carboxylicacid such as ammonium acetate and the like.

Based on 1 mole of the compound given by the formula (2), 1 to 3 mole ofthe cyanoacetic acid ester given by the formula (3), and 0.1 to 2 moleof the base are usually used.

The reaction temperature for the reaction is usually within a range fromroom temperature to 150° C., and the reaction time is usually within arange of from 10 minutes to 24 hours.

The reaction can be carried out removing the water generated from thereaction, for example, under the condition of azeotropic dehydration.

After completion of the reaction, the present compound can be obtainedby the work-up procedure such as pouring the reaction mixture intowater, extracting with an organic solvent, and concentrating the organiclayer; and, if necessary, the purification procedure such aschromatography and the like. The isomer of the present compoundoriginated from the substituents on the cyclopropane ring can beproduced by using the corresponding isomer of the compound given by theformula (2), and, if necessary, the purification procedure such aschromatography and the like.

The compound given by the formula (2) can be produced, for example, bymaking 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate given by theformula (4):

react with ozone (ozonolysis), or react with osmium tetraoxide—potassiummetaperiodate.

The compound given by the formula (4) is disclosed, for example, in EPpatent publication 1004569A1, and can be produced by the methoddescribed therein.

As the pests which can be controlled by the present compound, there ismentioned, example, arthropod such as insects, acarines and the like,specific examples of which are as follows:

Lepidoptera:

Pyralidae such as Chilo suppressalis (rice stem borer), Cnaphalocrocismedinalis (rice leafroller) and Plodia interpunctella (Indian mealmoth); Noctuidae such as Spodoptera litura (tobacco cutworm),Pseudaletia separata (rice armyworm) and Mamestra brassicae (cabbagearmyworm); Pieridae such as Pieris rapae crucivora (common cabbageworm);Tortricidae such as Adoxophyes spp.; Carposinidae; Lyonetiidae;Lymantriidae; Plusiinae; Agrotis spp. such as Agrotis segetum (turnipcutworm) and Agrotis ipsilon (black cutworm); Helicoverpa spp.; Heliotisspp.; Plutella xylostella (diamondback moth); Parnara guttata (riceskipper); Tinea pellionella (casemaking clothes moth); Tineolabisselliella (webbing clothes moth); and so on;

Diptera:

Culex spp. such as Culex pipiens pallens (common mosquito) and Culextritaeniorhynchus; Aedes spp. such as Aedes aegypti and Aedesalbopictus; Anopheles spp. such as Anopheles sinensis; Chironomidae(midges); Muscidae such as Musca domestica (housefly), Muscina stabulans(false stablefly) and Fannia canicularis (little housefly);Calliphoridae; Sarcophagidae; Anthomyiidae such as Delia platura(seedcorn maggot) and Delia antiqua (onion maggot); Tephritidae (fluitflies); Drosophilidae; Psychodidae (moth flies); Phoridae; Tabanidae;Simuliidae (black flies); Stomoxyidae; Ceratopogonidae (biting midges);and so on;

Dictyoptera:

Blattella germanica (German cockroach), Periplaneta fuliginosa(smokybrown cockroach), Periplaneta americana (American cockroach),Periplaneta brunnea (brown cockroach), Blatta orientalis (orientalcockroach) and so on;

Hymenoptera:

Formicidae (ants); Vespidae (hornets); Bethylidae; Tenthredinidae(sawflies) such as Athalis rosae ruficornis (cabbage sawfly); and so on;

Siphonaptera:

Ctenocephalides canis (dog flea), Ctenocephalides felis (cat flea),Pulex irritans and so on;

Anoplura:

Pediculus humanus humanus (body louse), Pthirus pubis (crab louse),Pediculus capitis (head louse), Pediculus corporis and so on;

Isoptera:

Reticulitermes speratus; Coptotermes formosanus; and so on;

Hemiptera:

Delphacidae (planthoppers) such as Laodelphax striatellus (small brownplanthopper), Nilaparvata lugens (brown planthopper) and Sogatellafurcifere (white backed rice planthopper); leafhoppers such asNephotettix cincticeps, Nephotettix virescens; Aphididae (aphids); plantbugs; Aleyrodidae (whiteflies); scales; Tingidae (lace bugs); Psyllidae;and so on;

Coleoptera (beetles):

Attagenus unicolor japonicus (black carpet beetle) and Authrenusverbasci (varied carpet beetle); corn rootworms such as Diabroticavirgifera (western corn rootworm) and Diabrotica undecimpunctata howardi(southern corn rootworm); Scarabaeidae such as Anomala cuprea (cupreouschafer) and Anomala rufocuprea (soybeen beatle); weevils such asSitophilus zeamais (maize weevil), Lissorhoptrus oryzophilus (ricewaterweevil), ball weevil and Callosobruchus chinensis (adzuki bean weevil);Tenebrionidae (darkling beetles) such as Tenebrio molitor (yellowmealworm) and Tribolium castaneum (red flour beetle); Chrysomelidae(leaf beetles) such as Oulema oryzae (rice leaf beetle), Phyllotretastriolata (striped flea beetle) and Aulacophora femoralis (cucurbit leafbeetle); Anobiidae; Epilachna spp. such as Epilachna vigintioctopunctata(twenty-eight-spotted ladybird); Lyctidae (powderpost beetles);Bostrychidae (false powderpost beetles); Cerambycidae; Paederus fuscipes(robe beetle); and so on;

Thysanoptera:

Thrips palmi, Flankliniella occidentalis (western flower thrips), Thripshawaiiensis (flower thrips) and so on;

Orthoptera:

Gryllotalpidae (mole crickets); Acrididae (grasshoppers); and so on;

Acarina:

Dermanyssidae such as Dermatophagoides farinae (American house dustmite) and Dermatophagoides pteronyssinus; Acaridae such as Tyrophagusputrescentiae (mold mite) and Aleuroglyphus ovatus; Glycyphagidae suchas Glycyphagus privatus, Glycyphagus domesticus and Glycyphagusdestructor; Cheyletidae such as Chelacaropsis malaccensis and Cheyletusfortis; Tarsonemidae; Chortoglyphus spp.; Haplochthonius spp.;Tetranychidae such as Tetranychus urticae (carmine spider mite),Tetranychus kanzawai (Kanzawa spider mite), Panonychus citri (citrus redmite) and Panonychus ulmi (European red mite); Ixodidae such asHaemaphysalis longiconis; and so on.

The pesticidal composition of the present invention may be the presentcompound itselt, but it is usually the formulations supported thepresent compound on carriers.

The examples of the formulations include oil solutions, emulsifiableconcentrates, wettable powders, flowable formulations (e.g. aqueoussuspension, aqueous emulsion), dusts, granules, aerosols, volatileformulations by heating (e.g. mosquito-coil, mosquito-mat for electricheating, volatile formulations with absorptive wick for heating),heating fumigants (e.g. self-burning type fumigants, chemical reactiontype fumigant, porous ceramic plate fumigant), non-heating volatileformulations (e.g. resin volatile formulations, impregnated papervolatile formulations), smoking formulations (e.g. fogging), ULVformulations and poisonous baits.

The formulation methods are, for example, as follows.

-   (1) A method for preparing the uniform mixing composition by adding    the present compound into a liquid carrier and/or gaseous carrier,    optionally with auxiliaries for formulation such as surfactants and    the like, and mixing.-   (2) A method for preparing the mixing composition by adding the    present compound into powdered solid carrier, optionally with with    auxiliaries for formulation such as surfactants and the like, and    mixing.-   (3) A method of impregnating a molded base material; or adding the    present compound into powdered solid carrier, optionally with with    auxiliaries for formulation such as surfactants and the like,    mixing, and molding.

The content of the present compound depends on the type of formulations,but these formulations usually contain 0.001 to 95% by weight of thepresent compound.

Examples of the carrier to be used for the formulation include solidcarriers such as clays (e.g. kaolin clay, diatomaceous earth, synthetichydrated silicon oxide, bentonite, Fubasami clay, acid clay), talc andthe like, ceramics, other inorganic minerals (e.g. sericite, quartz,sulfur, active carbon, calcium carbonate, hydrated silicon oxide,montmorillonite) and chemical fertilizers (e.g. ammonium sulfate,ammonium phosphate, ammonium nitrate, urea, ammonium chloride); liquidcarriers such as water, alcohols (e.g. methanol, ethanol), ketones (e.g.acetone, methyl ethyl ketone), aromatichydrocarbons (e.g. benzene,toluene, xylene, ethylbenzene, methylnaphthalene, phenylxylylethane),aliphatic hydrocarbons (e.g. hexane, cyclohexane, kerosene, gas oil),esters (ethyl acetate, butyl acetate), nitriles (e.g. acetonitrile,isobutyronitrile), ethers (e.g. diisopropyl ether, dioxane), acid amides(e.g. N,N-dimethylformamide, N,N-dimethylacetamide), halogenatedhydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride),dimethyl sulfoxide, vegetable oils (e.g. soybean oil, cottonseed oil);and gaseous carriers such as flon gas, butane gas, LPG (liquefiedpetroleum gas), dimethyl ether and carbon dioxide.

Examples of the surfactant include alkyl sulfates, alkylsulfonate salts,alkylarylsulfonate salts, alkyl aryl ethers, polyoxyethylene compoundsof alkyl aryl ethers, polyethylene glycol ethers, polyhydric alcoholesters and sugar alcohol derivatives.

Examples of the other auxiliaries for formulation include stickingagents, dispersing agents and stabilizers, typically casein, gelatin,polysaccharides (e.g. starch, gum arabic, cIulose ves,alginic acid),lignin derivatives, bentonite and synthetic water-soluble polymers (e.g.polyvinyl alcohol, polyvinylpyrrolidone), polyacrylic acid, BHT(2,6-di-tert- butyl-4-methyphenol) and BHA (mixture of2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).

An example of the solid base material of the mosquito-coil is a mixtureof raw plant powder such as wood powder and Pyrethrum marc and a bindingagent like Tabu powder (powder of Machilus thunbergii), starch orgluten.

An example of the molded base material of the mosquito-mat for electricheating is a plate of compacted fibrils of cotton linters or a mixtureof pulp and cotton linters.

The base material of the self-burning type fumigant includes, forexample, exothermic agents (e.g. nitrates, nitrites, guanidine salts,potassium chlorate, nitrocellulose, ethylcellulose, wood powder),pyrolytic stimulating agents (e.g. alkali metal salts, alkaline earthmetal salts, dichromates and chromates), oxygen sources (e.g. potassiumnitrate), combustion assistants (e.g. melanin, wheat starch), bulkfillers (e.g. diatomaceous earth) and binding agents (e.g. syntheticglue).

The base material of the chemical reaction type fumigant includes, forexample, an exothermic agents (e.g. alkali metal sulfides, polysulfides,hydrogensufides, calcium oxide), catalytic agents (e.g. carbonaneoussubstances, iron carbide and activated clay), organic foaming agents(e.g. azodicarbonamide, benzenesulfonylhydrazide,dinitrosopentamethylene tetramine, polystyrene, polyurethane) andfillers (e.g. natural or synthetic fibers).

Examples of the base material of the non-heating volatile formulationinclude thermoplastic resins and paper (e.g. filter paper, Japanesepaper).

The base material of the poisonous bait includes bait components (e.g.grain powder, vegetable oil, sugar, crystalline cellulose), antioxidants(e.g. dibutylhydroxytoluene, nordihydroguaiaretic acid), preservatives(e.g. dehydroacetic acid), substances for preventing erroneous eatingfrom children and pets (e.g. red pepper powder), pest-attractant flavors(e.g. cheese flavor, onion flavor, peanut oil).

The method for controlling pests of the present invention is usuallycarried out by applying the pesticidal composition of the presentinvention to the pests or a place where the pests inhabit.

The application methods of the pesticidal composition of the presentinvention are, for example, given below. The methods are suitablyselected according to the type of the pesticidal composition orapplication places.

-   (1) A method of applying the formulation as it is to pests or a    place where the pests inhabit.-   (2) A method of diluting the formulation with a solvent such as    water, and then applying it to pests or a place where the pests    inhabit.-   (3) A method of vaporizing the present compound at a place where the    pests inhabit with the formulation under normal temperature or    heating condition.

In the case of (2), the concentration of the dilution is usually 0.1 to10000 ppm.

The dosage of the present compound can be determined appropriately by atype of the formulation, a time of application, a place of application,a method of application, a species of pests, a damage level and so on inevery case. In the case of treating plane, it is usually in a range of 1to 10000 mg per 1 m² of the application area; and in the case oftreating space, it is usually in a range of 0.1 to 5000 mg per 1 m3 ofapplication space.

The pesticidal composition of the present invention can be used bycombinatinon use or simultaneous use with the other insecticide,nematocide, soil-pest controlling agent, fungicide, herbicide, plantgrowth regulator, repellent, synergist, fertilizer or soil conditionerunder pre-mixed conditions or non-mixed conditions.

Examples of the active ingredients of the insecticide and acaricideinclude organophosphorus compounds such as fenitrothion, fenthion,diazinon, chlorpyrifos, acephate, methidathion, disulfoton, DDVP,sulprofos, cyanophos, dioxabenzofos, dimethoate, phenthoate, malathion,trichlorfon, azinphos-methyl, monocrotophos and ethion; carbamatecompounds such as BPMC, benfuracarb, propoxur, carbosulfan, carbaryl,methomyl, ethiofencarb, aldicarb, oxamyl and fenothiocarb; pyrethroidcompounds such as etofenprox, fenvalerate, esfenvalerate, fenpropathrin,cypermethrin, permethrin, cyhalothrin, deltamethrin, cycloprothrin,fluvalinate, bifenthrin, 2-methyl-2-(4-bromodifluoromethoxyphenyl)propyl3-phenoxybenzyl ether, tralomethrin, silafluofen, d-phenothrin,cyphenothrin, d-resmethrin, acrinathrin, cyfluthrin, tefluthrin,transfluthrin, tetramethrin, allethrin, prallethrin, empenthrinimiprothrin, d-furamethrin and 5-(2-propynyl)furfuryl2,2,3,3-tetramethylcyclopropanecarboxylate; nitroimidazolidinederivatives; N-cyanoamidine derivatives such asN-cyano-N′-methyl-N′-(6-chloro-3-pyridylmethyl)acetoamidine; chlorinatedhydrocarbons such as endosulfan, a-BHC and1,1-bis(chlorophenyl)-2,2,2-trichloroethanol; benzoylphenylureacompounds such as chlorfluazuron, teflubenzuron and flufenoxuron;phenylpyrazole; metoxadiazon; bromopropylate; tetradifon;chinomethionat; pyridaben; fenpyroximate; diafenthiuron; tebufenpyrad;polynactins complex such as tetranactin, dinactin and trinactin;pyrimidifen; milbemectin; abamectin; ivermectin; and azadirachtin.

Examples of the repellent include 3,4-caranediol, N,N-diethyl-m-toluamide, 1-methylpropyl 2-(2-hydroxyethyl)-1-piperidinecarboxylate,p-menthan-3,8-diol and botanical essential oils (e.g. hyssop oil).

Examples of the synergist include bis(2,3,3,3-tetrachloropropyl) ether(S-421), N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide(MGK-264) and

-   5-[[2-(2-butoxyethoxy)ethoxy]methyl]-6-propyl-1,3-benzodiox ole    (piperonyl butoxide).

The present invention is explained by production example, formulationexamples, test example and so on, and the present invention is notrestricted by these examples.

First, the production examples of the present compound are shown.

PRODUCTION EXAMPLE 1

Into 10 ml of benzene were dissolved 1.0 g of4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-formylcyclopropanecarboxylate produced according to theReference Production Example below and 0.32 g of ethyl cyanoacetate, 0.2g of ammonium acetate was added to the mixture, and the mixture wasstirred for 1 hour under the condition of azeotropic dehydration withheating. The reaction mixture was cooled to room temperature, pouredinto water, and extracted with ethyl acetate. The organic layers werewashed with water and saturated sodium chloride aqueous solution insequence, dried over anhydrous sodium sulfate, and concentrated underreduced pressure. The obtained residue was subjected to silica gelcolumn chromatography to obtain 0.96 g of4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-((E)-2-cyano-3-ethoxy-3-oxo-1-propenyl)cyclopropanecarboxylate (78%) (hereinafter, referred to as PresentCompound 1).

The physical property data of Present Compound 1

¹H-NMR (CDCl₃, TMS) ä (ppm): 1.32 (s, 3H), 1.34 (t, 3H), 1.40 (s, 3H),2.08 (d, 1H), 2.65 (dd, 1H), 3.42 (s, 3H), 4.29 (q, 2H), 4.59 (s, 2H),5.27 (s, 2H), 7.27 (d, 1H)

PRODUCTION EXAMPLE 2

Into 10 ml of benzene were dissolved 1.0 g of4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-formylcyclopropanecarboxylate produced according to theReference Production Example below and 0.28 g of methyl cyanoacetate,0.2 g of ammonium acetate was added to the mixture, and the mixture wasstirred for 1 hour under the condition of azeotropic dehydration withheating. The reaction mixture was cooled to room temperature, pouredinto water, and extracted with ethyl acetate. The organic layers werewashed with water and saturated sodium chloride aqueous solution insequence, dried over sodium sulfate, and concentrated under reducedpressure. The obtained residue was subjected to silica gel columnchromatography to obtain 0.71 g of4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-((E)-2-cyano-3-methoxy-3-oxo-1-propenyl)cyclopropanecarboxylate (59%) (hereinafter, referred to as PresentCompound 2).

The physical property data of Present Compound 2

¹H-NMR (CDCl₃, TMS) ä (ppm): 1.30 (s, 3H), 1.39 (s, 3H), 2.07 (d, 1H),2.65 (dd, 1H), 3.40 (s, 3H), 3.86 (s, 3H), 4.58 (s, 2H), 5.27 (s, 2H),7.27 (d, 1H)

PRODUCTION EXAMPLE 3

By the similar method to the Production Example 1 except for using 0.36g of propyl cyanoacetate instead of 0.32 g of ethyl cyanoacetate wasobtained 0.59 g of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-((E)-2-cyano-3-propoxy-3-oxo-1-propenyl)cyclopropanecarboxylate (hereiafter, referred to as Present Compound 3).

The physical property data of Present Compound 3

¹H-NMR (CDCl₃, TMS) ä (ppm): 0.96 (t, 3H), 1.32 (s, 3H), 1.39 (s, 3H),1.75 (m, 2H), 2.08 (d, 1H), 2.65 (dd, 1H), 3.39 (s, 3H), 4.20 (t, 2H),4.59 (s, 2H), 5.27 (s, 2H), 7.26 (d, 1H)

PRODUCTION EXAMPLE 4

By the similar method to the Production Example 1 except for using 0.36g of allyl cyanoacetate instead of 0.32 g of ethyl cyanoacetate wasobtained 0.88 g of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-((E)-2-cyano-3-allyloxy-3-oxo-1-propenyl)cyclopropanecarboxylate (hereiafter, referred to as Present Compound 4).

The physical property data of Present Compound 4

¹H-NMR (CDCl₃, TMS) ä (ppm): 1.32 (s, 3H), 1.39 (s, 3H), 2.09 (d, 1H),2.66 (dd, 1H), 3.40 (s, 3H), 4.59 (s, 2H), 4.73 (d, 2H), 5.28 (s, 2H),5.32 (dd, 2H), 5.94 (m, 1H), 7.27 (d, 1H)

PRODUCTION EXAMPLE 5

By the similar method to the Production Example 1 except for using 0.36g of isopropyl cyanoacetate instead of 0.32 g of ethyl cyanoacetate wasobtained 1.08 g of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-((E)-2-cyano-3-isopropoxy-3-oxo-1-propenyl)cyclopropanecarboxylate (hereiafter, referred to as Present Compound 5).

The physical property data of Present Compound 5

¹H-NMR (CDCl₃, TMS) ä (ppm): 1.30 (d, 6H), 1.32 (s, 3H), 1.40 (s, 3H),2.12 (d, 1H), 2.65 (dd, 1H), 3.42 (s, 3H), 4.59 (s, 2H), 5.13 (m, 1H),5.27 (s, 2H), 7.24 (d, 1H)

PRODUCTION EXAMPLE 6

By the similar method to the Production Example 1 except for using 0.40g of t-butyl cyanoacetate instead of 0.32 g of ethyl cyanoacetate wasobtained 1.15 g of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-((E)-2-cyano-3-t-butyloxy-3-oxo-1-propenyl)cyclopropanecarboxylate (hereiafter, referred to as Present Compound 6).

The physical property data of Present Compound 6

¹H-NMR (CDCl₃, TMS) ä (ppm): 1.30 (s, 3H), 1.41 (s, 3H), 1.52 (s, 9H),2.06 (d, 1H), 2.64 (dd, 1H), 3.43 (s, 3H), 4.59 (s, 2H), 5.27 (s, 2H),7.23 (d, 1H)

Next, the production example of the compound given by the formula (2) isshown as the reference example.

REFERENCE PRODUCTION EXAMPLE

Into 10 ml of tetrahydrofuran were dissolved 1.0 g of4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol and 0.42 g of ethylcyanoacetate, 0.9 g of3-(2-methyl-1-propenyl)-2-thy-cyclopropanecarboxylic chloride {ratio ofstereo isomer: (1R)-trans/(IR)-cis/(1S)-trans/(IS)-cis=93.9/2.5/3.5/0.1}was added to the mixture under ice-cooling, and the mixture was stirredfor 8 hours at room temperature. The reaction mixture was poured intoice-and-water, and extracted with 80 ml of ethyl acetate twice. Theorganic layers were combined, washed with saturated sodium chlorideaqueous solution, dried over anhydrous sodium sulfate, and concentratedunder reduced pressure. The obtained residue was subjected to silica gelcolumn chromatography to obtain 1.4 g of4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-(2-methyl-1-propenyl) cyclopropanecarboxylate given bythe formula (4).

¹H-NMR (CDCl₃, TMS) ä (ppm): 1.13 (s, 3H), 1.26 (s, 3H), 1.38 (d, 1H),1.69 (brs, 6H), 2.10 (dd, 1H), 3.40 (s, 3H), 4.59 (s, 2H), 4.87 (d, 1H),5.24 (dd, 2H)

Into the mixture of 25 ml of tetrahydrofuran and 150 ml of 1,4-dioxanewas dissolved 15.4 g of 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-(2-methyl-1-propenyl) cyclopropanecarboxylate, 1.0 g ofosmium tetraoxide and 50 ml of water dissolved 24.0 g of potassiummetaperiodate were added to the solution at room temperature, and themixture was stirred for 2 hours under reflux condition. The reactionmixture was poured into about 200 ml of water, extracted with 200 ml ofethyl acetate twice. The organic layers were combined, washed with 1%sodium thiosulfate aqueous solution, saturated sodium hydrogencarbonateaqueous solution, saturated sodium chloride aqueous solution insequence, dried over anhydrous sodium sulfaate, and concentrated underreduced pressure. The obtained residue was subjected to silica gelcolumn chromatography to obtain 10.4 g of4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-formylcyclopropanecarboxylate given by the formula (2).

¹H-NMR (CDCl₃, TMS) ä (ppm): 1.30 (s, 3H), 1.36 (s, 3H), 2.47 (m, 2H),3.41 (s, 3H), 4.59 (s, 2H), 5.26 (s, 2H), 9.59 (s, 1H)

Next, the formulation examples are shown. “Parts” means parts by weight.

FORMULATION EXAMPLE 1

Twenty parts of Present Compound 1 to 6 are dissolved in 65 parts ofxylene. Fifteen parts of Sorpol 3005X (registered trademark of TohoChemical) are added thereto, stirred and mixed well to give emulsifiableconcentrate.

FORMULATION EXAMPLE 2

Five parts of Sorpol 3005X are added to 40 parts of Present Compound 1to 6 and mixed well. Thirty-two parts of Carplex #80 (synthetic hydratedsilica, registered trademark of Shionogi & Co.) and 23 parts of 300-meshdistomaceous earth are added thereto and mixed well with a juice mixerto give wettable powders.

FORMULATION EXAMPLE 3

A mixture of 10 parts of Present Compound 1 to 6, 10 parts ofphenylxylylethane and 0.5 part of Sumidur L-75 (tolylenediisocyanatemanufactured by Sumitomo Bayer Urethane Co., Ltd.) is added to 20 partsof a 10% aqueous solution of gum arabic, and stirred with a homomixer togive an emulsion having the mean particle diameter of 20 μm. Two partsof ethylene glycol are added thereto and stirred 24 hours on a waterbath of 60° C. to give a microcapsule slurry. A thickening agentsolution is prepared by dispersing 0.2 part of xanthan gum and 1.0 partof Beagum R (aluminum magnesium silicate manufactured by Sanyo ChemicalCo., Ltd.) in 56.3 parts of ion-exchanged water. Forty-two and a half(42.5) parts of the above microcapsule slurry and 57.5 parts of theabove thickening agent solution are mixed to give microencapsulatedformulation.

FORMULATION EXAMPLE 4

A mixture of 10 parts of Present Compound 1 to 6 and 10 parts ofphenylxylylethane is added to 20 parts of a 10% aqueous solution ofpolyethylene glycol and stirred with a homomixer to give an emulsionhaving the mean particle diameter of 3 im. Two-tenth (0.2) part ofxanthan gum and 1.0 part of Beagum R (aluminum magnesium silicatemanufactured by Sanyo Chemical Co., Ltd.) are dispersed in 58.8 parts ofion-exchanged water to give a thickening agent solution. Forty parts ofthe above emulsion and 60 parts of the above thickening agent solutionare mixed to give flowable formulation.

FORMULATION EXAMPLE 5

Five parts of Present Compound 1 to 6 are mixed with 3 parts of Carplex#80 (fine powder of synthetic hydrated silicon dioxide, trademark ofShionogi & Co.), 0.3 parts of PAP (mixture of monoisopropyl phosphateand diisopropyl phosphate) and 91.7 parts of 300-mesh talc, and stirredwith a juice mixer to give dusts.

FORMULATION EXAMPLE 6

One-tenth (0.1) part of Present Compound 1 to 6 is dissolved in 5 partsof dichloromethane and mixed with 94.9 parts of deodorized kerosene togive oil solution.

FORMULATION EXAMPLE 7

An aerosol vessel is filled with the solution obtained by dissolving 1part of Present Compound 1 to 6 with 5 parts of dichloromethane and 34parts of deodorized kerosene. The vessel is then equipped with a valveand 60 parts of propellant (liquefied petroleum gas) are charged throughthe valve into the aerosol vessel under pressure to give oil-basedaerosol.

FORMULATION EXAMPLE 8

An aerosol vessel is filled with 50 parts of water and a mixture of 0.6part of Present Compound 1 to 6, 5 parts of xylene, 3.4 parts ofdeodorized kerosene and 1 part of Atmos 300 (emulsifier, trademark ofAtlas Chemical Co.). The vessel is then equipped with a valve and 40parts of propellant (liquefied petroleum gas) is charged through thevalve into the aerosol vessel under pressure to give water-basedaerosol.

FORMULATION EXAMPLE 9

A solution prepared by dissolving 0.3 g of Present Compound 1 to 6 in 20ml of acetone is homogeneously mixed with 99.7 g of a carrier for amosquito-coil (mixture of Tabu powder, Pyrethrum marc and wood powder atthe ratio of 4:3:3). After 100 ml of water is added, the mixture iskneaded well, molded and dried to give mosquito-coil.

FORMULATION EXAMPLE 10

Ten milliliters (10 ml) of solution is prepared by dissolving 0.8 g ofPresent Compound 1 to 6 and 0.4 g of piperonyl butoxide in acetone. 0.5ml of the obtained solution is impregnated with a base material (a plateof compacted fibrils of a mixture of pulp ahd cotton linter: 2.5 cm×1.5cm×0.3 cm of thichness) homogeneously to give mosquito-mat.

FORMULATION EXAMPLE 11

Three parts of Present Compound 1 to 6 is dissolved in 97 parts ofdeodorized kerosene. The obtained solution is charged in a vessel ofpolyvinyl chloride. In the vessel is inserted a porous absorptive wickwhich is inorganic powder solidified with a binder and then calcined,the upper portion of which wick can be heated with a heater, to give apart of an electric heating fumigation device.

FORMULATION EXAMPLE 12

A solution prepared by dissolving 100 mg of Present Compound 1 to 6 inan appropriate amount of acetone is impregnated with a porous ceramicplate (4.0 cm×4.0 cm×1.2 cm of thickness) to give fumigant for heating.

FORMULATION EXAMPLE 13

A solution prepared by dissolving 100 ig of Present Compound 1 to 6 inan appropriate amount of acetone is applied onto filter paper (2.0cm×2.0 cm×0.3 mm of thickness) and the acetone is vaporized to givevolatile agent for using at room temperature.

FROMULATION EXAMPLE 14

A acetone solution of Present Compound 1 to 6 is impregnated with a testsheet to be 1 g of the present compound per 1 m², and the acetone isvaporized to give an acaricidal sheet.

Next, the following test example shows that present compound is usefulas an active ingredient of a pesticidal composition.

TEST EXAMPLE 1

A solution of 0.025 part of Present Compound 1 to 6 dissolved with 10parts of dichloromethane was mixed with 89.9975 parts of deodorizedkerosene to give a 0.025% oil solution.

Adult houseflies (5 males and 5 females) were left in a cubic chamber(70 cm at side). Seven-tenths (0.7) ml of the 0.025% oil solution ofPresent Compound 1 to 6 prepared above was sprayed with a spray gun at apressure of 8.8×10⁴ Pa from a small window on the side of the chamber.Then, the number of the knocked-down insects was counted at times for 10minutes. The time for knocking down half of the tested insects (KT₅₀)was calculated from the result.

Furthermore, the test was similarly done by using(4-methoxymethyl-2,3,5,6-tetrafluoro)phenylmethyl [1R[1α,3β(Z)]]-2,2-dimethyl-3-(2-fluoro-3-methoxy-3-oxopropenyl)cyclopropanecarboxylate(hereinafter, referred to as Comparative Compound):

described in GB patent publication 2,268,740 as a comparative compound.The tests were done twice repeat, and the KT₅₀ values were calculatedfrom the averages.

The results are shown in Table 1.

TABLE 1 Testing compounds KT₅₀ (minutes) Present Compound 1 1.5 PresentCompound 2 1.9 Present Compound 3 4.1 Present Compound 4 4.3 PresentCompound 5 1.5 Present Compound 6 3.4 Comparative Compound >10

INDUSTRIAL APPLICABILITY

By using the present compounds, pests can be controlled.

1. A4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-(2-cyano-3-hydrocarbyloxy-3-oxo-1-propenyl)cyclopropanecarboxylate given by the formula (1):

wherein G represents C1–C4 alkyl or C3–C4 alkenyl.
 2. The4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-(2-cyano-3-hydrocarbyloxy-3-oxo-1-propenyl)cyclopropanecarboxylate according to claim 1, wherein the relativeconfiguration between the substituents at 1-position and 3-position onthe cyclopropane ring is trans-configuration with 80% or more ratio inthe formula (1).
 3. The 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-(2-cyano-3-hydrocarbyloxy-3-oxo-1-propenyl)cyclopropanecarboxylate according to claim 1, wherein the relativeconfiguration between the substituents at 1-position and 3-position onthe cyclopropane ring is trans-configuration in the formula (1).
 4. Apesticidal composition containing an effective amount of the4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-(2-cyano-3-hydrocarbyloxy-3-oxo-1-propenyl)cyclopropanecarboxylate given by the formula (1):

wherein G represents C1–C4 alkyl or C3–C4 alkenyl.
 5. A method ofcontrolling pests comprising applying an effective amount of the4-methoxymethyl-2,3,5,6-tetrafluorobenzyl2,2-dimethyl-3-(2-cyano-3-hydrocarbyloxy-3-oxo-l-propenyl)cyclopropanecarboxylate given by the formula (1) to pests or the habitatof the pests:

wherein G represents C1–C4 alkyl or C3–C4 alkenyl.